Polymeric compositions, method for their preparation, and lubricants containing them

ABSTRACT

Compositions useful as multi-purpose lubricant and functional fluid additives and as thickeners and antisag additives for resins, paints and the like are prepared by free radical polymerization of at least one ethylenically unsaturated monomer in the presence of an oil-soluble dispersant. The carboxylic dispersants are preferred, especially esters of hydrocarbon-substituted succinic acids wherein the substituent contains at least about 30 carbon atoms and the reaction products of such acids or their derivatives with amines, usually polyalkylene polyamines.

This application is a division of copending application Ser. No.433,322, filed Jan. 14, 1974.

This invention relates to new compositions of matter useful as additivesfor lubricants, fuels, resins and the like, and to methods for theirpreparation. More particularly, it relates to compositions prepared bypolymerizing, under free radical polymerization conditions, (A) at leastone ethylenically unsaturated monomer in the presence of (B) at leastone oil-soluble dispersant characterized by the presence of anoil-solubilizing group containing at least about 30 aliphatic carbonatoms and a polar group bonded thereto.

The preparation of multi-purpose lubricant and functional fluidadditives is of continuing importance. In particular, it is oftendesired to modify the properties of dispersants and the like, as byproviding them with viscosity modifying or extreme pressure propertiesas well as dispersant properties. It is also of interest to developthickeners, anti-sag agents and the like for paints and resins.

A principal object of this invention, therefore, is to prepare newpolymeric compositions of matter.

A further object is to prepare multi-purpose compositions for use inlubricants, functional fluids and fuels.

A further object is to prepare compositions which impart favorableproperties to resin and plastic systems.

Other objects will in part be obvious and will in part appearhereinafter.

Reagent A used in the method of this invention is at least oneethylenically unsaturated monomer. Many of such monomers are, of course,known and any of these may be used. They include (1) unsaturatedmonohydric alcohols and esters thereof, (2) unsaturated carboxylic acidsand esters thereof, (3) unsaturated polyhydric alcohols and estersthereof, (4) vinyl cyclic compounds, (5) unsaturated ethers, (6)unsaturated ketones, (7) unsaturated amides, (8) unsaturated aliphatichydrocarbons, (9) alkenyl halides, (10) unsaturated acid anhydrides,(11) unsaturated acid halides, and (12) unsaturated nitriles. Specificillustrations of such compounds are:

1. Unsaturated alcohols and esters thereof: Allyl, methallyl, crotyl,1-chloroallyl, 2-chloroallyl, cinnamyl, vinyl, methylvinyl, 1-phenallyl,butenyl alcohols, and esters of such alcohols with saturated acids suchas acetic, propionic, butyric, valeric, caproic and stearic; withunsaturated acids such as acrylic, alpha-substituted acrylic (includingalkylacrylic, e.g., methacrylic, ethylacrylic, propylacrylic, etc., andarylacrylic such as phenylacrylic), crotonic, oleic, linoleic andlinolenic; with polybasic acids such as oxalic, malonic, succinic,glutaric, adipic, pimelic, suberic, azelaic and sebacic; withunsaturated polybasic acids such as maleic, fumaric, citraconic,mesaconic, itaconic, methylenemalonic, acetylenedicarboxylic andaconitic; and with aromatic acids, e.g., benzoic, phenylacetic,phthalic, terephthalic and benzoylphthalic acids.

2. Unsaturated acids (examples of which appear above) and esters thereofwith saturated alcohols, such as methyl, ethyl, propyl, isopropyl,butyl, isobutyl, secbutyl, tert-butyl, 2-ethylhexyl, cyclohexyl orbehenyl alcohols.

3. Unsaturated polyhydric alcohols, e.g., butenediol, and esters thereofwith saturated and unsaturated aliphatic and aromatic, monobasic andpolybasic acids, examples of which appear above.

4. Vinyl cyclic compounds including styrene, o-, m-, p-chlorostyrenes,bromostyrenes, fluorostyrenes, methylstyrenes, ethylstyrenes andcyanostyrenes; di-, tri-, and tetra-chlorostyrenes, bromostyrenes,fluorostyrenes, methylstyrenes, ethylstyrenes, cyanostyrenes;vinylnaphthalene, vinylcyclohexane, divinylbenzene, trivinylbenzene,allylbenzene, and heterocycles such as vinylfuran, vinylpyridine,vinylbenzofuran, N-vinylcarbazole, N-vinylpyrrolidone,N-vinylthiopyrrolidone and N-vinyloxazolidone.

5. Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether,cyclohexyl vinyl ether, octyl vinyl ether, diallyl ether, ethylmethallyl ether and allyl ethyl ether.

6. Unsaturated ketones, e.g., methyl vinyl ketone and ethyl vinylketone.

7. Unsaturated amides, such as acrylamide, methacrylamide,N-methylacrylamide, N-phenylacrylamide, N-allylacrylamide,N-methylolacrylamide, N-allylcaprolactam, diacetone acrylamide,hydroxymethylated diacetone acrylamide, N-(1,1-dimethyl-3-hydroxybutyl)acrylamide and 2-acrylamido-2-methylpropanesulfonic acid.

8. Unsaturated aliphatic hydrocarbons, for instance, ethylene,propylene, butenes, butadiene, isoprene, 2-chlorobutadiene andalpha-olefins in general.

9. Alkenyl halides, e.g., vinyl fluoride, vinyl chloride, vinyl bromide,vinylidene chloride, vinylidene bromide, allyl chloride and allylbromide.

10. Unsaturated acid anhydrides, e.g., maleic, citraconic, itaconic,cis-4-cyclohexene-1,2-dicarboxylic andbicyclo(2,2,1)-5-heptene-2,3-dicarboxylic anhydrides.

11. Unsaturated acid halides such as cinnamoyl, acrylyl, methacrylyl,crotonyl, oleyl and fumaryl chlorides or bromides.

12. Unsaturated nitriles, e.g., acrylonitrile, methacrylonitrile andother substituted acrylonitriles.

The preferred monomers for use as reagent A are those from the abovelist containing from 3 to about 10 carbon atoms and having a terminalolefinic bond, especially vinyl-type aromatic compounds (chieflysubstituted benzenes such as styrene, vinyltoluene and α-methylstyrene),vinyl-substituted nirogen-containing heterocyclic compounds (chieflylactams and their thio analogs such as N-vinylpyrrolidone andN-vinylthiopyrrolidone), vinly carboxylates (e.g., vinyl acetate, vinylpropionate), and acrylic monomers. By "acrylic monomers" is meantacrylic and methacrylic acids and their esters, amides and nitriles.Especially preferred are styrene, acrylonitrile and diacetoneacrylamide.

Reagent B, as previously indicated, is at least one oil-solubledispersant. The characterizing feature of the dispersant, with respectto molecular structure, is the presence of an oil-solubilizing groupcontaining at least about 30 aliphatic carbon atoms bonded directly to apolar group. The dispersant may contain more than one of either of suchgroups per molecule, as will be apparent from the descriptionhereinafter.

Many of the materials contemplated as reagent B are referred to as"ashless dispersants" although, depending on its constitution, thedispersant may upon combustion yield a non-volatile material such asboric oxide or phosphorus pentoxide. It does not, however, ordinarilycontain metal and therefore does not yield a metal-containing ash oncombustion.

Dispersants of this type are known in the art and are described invarious patents. Any of such dispersants are suitable for use inpreparing the compositions of this invention. The following areillustrative:

(1) Reaction products of carboxylic acids (or derivatives thereof)containing at least about 34 and preferably at least about 54 aliphaticcarbon atoms with nitrogen-containing compounds such as amines, ureasand hydrazines, with organic hydroxy compounds such as phenols andalcohols, and/or with basic inorganic materials. Examples of theseproducts, referred to herein as "carboxylic dispersants", are describedin British Pat. No. 1,306,529 and in many U.S. patents including thefollowing U.S. Pat. Nos.:

3,163,603

3,184,474

3,215,707

3,219,666

3,271,310

3,272,746

3,281,357

3,306,908

3,311,558

3,316,177

3,340,281

3,341,542

3,346,493

3,351,552

3,381,022

3,399,141

3,415,750

3,433,744

3,444,170

3,448,048

3,448,049

3,451,933

3,454,607

3,467,668

3,501,405

3,522,179

3,541,012

3,542,678

3,542,680

3,567,637

3,574,101

3,576,743

3,630,904

3,632,510

3,632,511

3,697,428

3,725,441

Re. 26,433

(2) Reaction products of aliphatic or alicyclic halides containing atleast about 30 carbon atoms with amines, preferably polyalkylenepolyamines. These may be characterized as "amine dispersants" andexamples thereof are described, for example, in the following U.S. Pat.Nos.:

3,275,554

3,438,757

3,454,555

3,565,804

(3) Reaction products of alkyl phenols in which the alkyl group containsat least about 30 carbon atoms with aliphatic C≧7 aldehydes (especiallyformaldehyde) and amines (especially polyalkylene polyamines), which maybe characterized as "Mannich dispersants". The materials described inthe following U.S. patents are illustrative, U.S. Pat. Nos.:

3,413,347

3,697,574

3,725,277

3,725,480

3,726,882

(4) Products obtained by post-treating the carboxylic, amine or Mannichdispersants with such reagents as urea, thiourea, carbon disulfide,aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinicanhydrides, nitriles, epoxides, boron compounds, phosphorus compounds orthe like. Exemplary materials of this kind are described in thefollowing U.S. Pat. Nos.:

3,036,003

3,087,936

3,200,107

3,216,936

3,254,025

3,256,185

3,278,550

3,280,234

3,281,428

3,282,955

3,312,619

3,366,569

3,367,943

3,373,111

3,403,102

3,442,808

3,455,831

3,455,832

3,493,520

3,502,677

3,513,093

3,533,945

3,539,633

3,573,010

3,579,450

3,591,598

3,600,372

3,639,242

3,649,229

3,649,659

3,658,836

3,697,574

3,702,757

3,703,536

3,704,308

3,708,522

The pertinent disclosures of all of the above-noted patents areincorporated by reference herein.

Especially useful as reagent B are dispersants having an averagemolecular weight no higher than about 5000. Of these, the carboxylicdispersants are preferred. They may be most conveniently and accuratelydescribed in terms of radicals I and II present therein. Radical I isusually an acyl, acyloxy or acylimidoyl radical containing at leastabout 34 carbon atoms. The structures of these radicals, as defined bythe International Union of Pure and Applied Chemistry, are as follows (Rrepresenting a hydrocarbon or similar group): ##STR1##

Radical II is preferably at least one radical in which a nitrogen oroxygen atom is attached directly to said acyl, acyloxy or acylimidoylradical, said nitrogen or oxygen atom also being attached to ahydrocarbon radical or substituted hydrocarbon radical. With respect toradical II, the dispersants are conveniently classified as"nitrogen-bridged dispersants" and "oxygen-bridged dispersants" whereinthe atom attached directly to radical I is nitrogen or oxygen,respectively.

The nitrogen-bridged dispersants, which will be described first, arethose disclosed (for example) in the above-mentioned U.S. Pat. Nos.3,219,666 and 3,272,746 which also describe a large number of methodsfor their preparation. The nitrogen-containing group therein is derivedfrom compounds characterized by a radical of the structure <NH whereinthe two remaining valences of nitrogen are satisfied by hydrogen, aminoor organic radicals bonded to said nitrogen atom through directcarbon-to-nitrogen linkages. These compounds include aliphatic,aromatic, heterocyclic and carbocyclic amines as well as substitutedureas, thioureas, hydrazines, guanidines, amidines, amides, thioamides,cyanamides and the like.

Especially preferred as nitrogen-containing compounds used in thepreparation of the nitrogen-bridged dispersants are alkylene polyaminesand hydroxyalkyl-substituted alkylene polyamines. The alkylenepolyamines comprise, in general, alkylene amines containing about 10 orless alkylene groups joined through nitrogen atoms. They includeprincipally the ethylene amines, propylene amines, butylene amines andhomologs thereof, and also piperazines and aminoalkyl-substitutedpiperazines. Hydroxyalkyl-substituted derivatives of these alkylenepolyamines are also contemplated for use in preparing thenitrogen-bridged dispersant. Typical examples of suitable amines areethylene diamine, triethylene tetramine, pentaethylene hexamine,propylene diamine, tripropylene tetramine, di-(trimethylene) triamine,1,4-bis-(2-aminoethyl)piperazine, 1-(2-aminopropyl)piperazine,N-(2-hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl)piperazine, and2-heptadecyl-1-(2-hydroxyethyl)-imidazoline. Also useful are thepolyoxyalkylene polyamines (e.g., "Jeffamines"). Mixtures of theseamines may also be used.

The preferred amines are the polyethylene polyamines containing from twoto about eight amino groups per molecule. A commercially availablemixture of polyethylene polyamines containing an average of about 3-7amino groups per molecule is particularly suitable.

The source of radical I in the nitrogen-bridged dispersant is anacylating agent comprising a carboxylic acid-producing compoundcontaining a hydrocarbon or substituted hydrocarbon substituent whichhas at least about 30 and preferably at least about 50 carbon atoms. By"carboxylic acid-producing compound" is meant an acid, anhydride, acidhalide, ester, amide, imide, amidine or the like; the acids andanhydrides are preferred.

The carboxylic acid-producing compound is usually prepared by thereaction (more fully described hereinafter) of a relatively lowmolecular weight carboxylic acid or derivative thereof with ahydrocarbon source containing at least about 30 and preferably at leastabout 50 carbon atoms. The hydrocarbon source is usually aliphatic andshould be substantially saturated, i.e., at least about 95% of the totalnumber of carbon-to-carbon covalent linkages should be saturated. Itshould also be substantially free from pendant groups containing morethan about six aliphatic carbon atoms. It may be a substitutedhydrocarbon source; by "substituted" is meant sources containingsubstituents which do not alter significantly their character orreactivity. Examples are halide, hydroxy, ether, keto, carboxy, ester(especially lower carbalkoxy), amide, nitro, cyano, sulfoxy and sulfoneradicals. The substituents, if present, generally comprise no more thanabout 10% by weight of the hydrocarbon source.

The preferred hydrocarbon sources are those derived from substantiallysaturated petroleum fractions and olefin polymers, particularly polymersof monoolefins having from 2 to about 30 carbon atoms. Thus, thehydrocarbon source may be derived from a polymer of ethylene, propene,1-butene, isobutene, 1-octene, 3-cyclohexyl-1-butene, 2-butene,3-pentene or the like. Also useful are interpolymers of olefins such asthose illustrated above with other polymerizable olefinic substancessuch as styrene, chloroprene, isoprene, p-methylstyrene, piperylene andthe like. In general, these interpolymers should contain at least about80%, preferably at least about 95%, on a weight basis of units derivedfrom the aliphatic monoolefins.

Another suitable hydrocarbon source comprises saturated aliphatichydrocarbons such as highly refined high molecular weight white oils orsynthetic alkanes.

In many instances, the hydrocarbon source should contain an activatingpolar radical to facilitate its reaction with the low molecular weightacid-producing compound. The preferred activating radicals are halogenatoms, especially chlorine, but other suitable radicals include sulfide,disulfide, nitro, mercaptan, ketone and aldehyde groups.

As already pointed out, the hydrocarbon sources generally contain atleast about 30 and preferably at least about 50 carbon atoms. Among theolefin polymers those having a molecular weight of about 700-5000 arepreferred, although higher polymers having molecular weights from about10,000 to about 100,000 or higher may sometimes be used. Especiallysuitable as hydrocarbon sources are isobutene polymers within theprescribed molecular weight range, and chlorinated derivatives thereof.

Any one of a number of known reactions may be employed for thepreparation of the carboxylic acid-producing compound. Thus, an alcoholof the desired molecular weight may be oxidized with potassiumpermanganate, nitric acid or a similar oxidizing agent; a halogenatedolefin polymer may be reacted with a ketene; an ester of an activehydrogen-containing acid, such as acetoacetic acid, may be converted toits sodium derivative and the sodium derivative reacted with ahalogenated high molecular weight hydrocarbon such as brominated wax orbrominated polyisobutene; a high molecular weight olefin may beozonized; a methyl ketone of the desired molecular weight may beoxidized by means of the haloform reaction; an organometallic derivativeof a halogenated hydrocarbon may be reacted with carbon dioxide; ahologenated hydrocarbon or olefin polymer may be converted to a nitrile,which is subsequently hydrolyzed; or an olefin polymer or itshalogenated derivative may undergo a reaction with an unsaturatedcarboxylic acid or derivative thereof such as acrylic acid, methacrylicacid, maleic acid, maleic anhydride, fumaric acid, itaconic acid,itaconic anhydride, citraconic acid, citraconic anhydride, mesaconicacid, glutaconic acid, chloromaleic acid, aconitic acid, crotonic acid,methylcrotonic acid, sorbic acid, 3-hexenoic acid, 10-decenoic acid,2-pentene-1,3,5-tricarboxylic acid, and the like, or with ahalogen-substituted carboxylic acid or derivative thereof. This latterreaction is preferred, especially when the acid-producing compound isunsaturated and preferably when it is maleic acid or anhydride. Theresulting product is then a hydrocarbon-substituted succinic acid orderivative thereof. The reaction leading to its formation involvesmerely heating the two reactants at about 100°-200° C. The substitutedsuccinic acid or anhydride thus obtained, may, if desired, be convertedto the corresponding acid halide by reaction with known halogenatingagents such as phosphorus trichloride, phosphorus pentachloride orthionyl chloride.

For the formation of the nitrogen-bridged dispersant, thehydrocarbon-substituted succinic anhydride or acid, or other carboxylicacid-producing compound, and the alkylene polyamine or othernitrogen-containing reagent are heated to a temperature above about 80°C., preferably about 100°-250° C. The product thus obtained haspredominantly amide, imide and/or amidine linkages (containing acyl oracylamidoyl groups). The process may in some instances be carried out ata temperature below 80° C. to produce a product having predominantlysalt linkages (containing acyloxy groups). The use of a diluent such asmineral oil, benzene, toluene, naphtha or the like is often desirable tofacilitate control of the reaction temperature.

The relative proportions of the carboxylic acid-producing compound andthe alkylene polyamine or the like are such that at least about one-halfthe stoichiometrically equivalent amount of polyamine is used for eachequivalent of carboxylic acid-producing compound. In this regard it willbe noted that the equivalent weight of the alkylene polyamine is basedupon the number of amine radicals therein, and the equivalent weight ofthe carboxylic acid-producing compound is based on the number of acidicor potentially acidic radicals. (Thus, the equivalent weight of ahydrocarbon-substituted succinic acid or anhydride is one-half itsmolecular weight.) Although a minimum of one-half equivalent ofpolyamine per equivalent of acylating agent should be used, there doesnot appear to be an upper limit for the amount of polyamine. If anexcess is used, it merely remains in the product unreacted without anyapparent adverse effects. Ordinarily, about 1-2 equivalents of polyamineare used per equivalent of acylating agent.

In an alternative method for producing the nitrogen-bridged dispersant,the alkylene polyamine is first reacted with a low molecular weight,unsaturated or halogen-substituted carboxylic acid or derivative thereof(such as maleic anhydride or one of the others previously mentioned) andthe resulting intermediate is subsequently reacted with the hydrocarbonsource as previously described.

Oxygen-bridged dispersants comprise the esters of the above-describedcarboxylic acids, as described (for example) in the aforementioned U.S.Pat. Nos. 3,381,022 and 3,542,678. As such, they contain acyl or,occasionally, acylimidoyl radicals as radical I. (An oxygen-bridgeddispersant containing an acyloxy radical as radical I would be aperoxide, which is unlikely to be stable under all conditions of use ofthe compositions of this invention.) These esters are preferablyprepared by conventional methods, usually the reaction (frequently inthe presence of an acidic catalyst) of the carboxylic acid-producingcompound with an aliphatic compound such as a monohydric or polyhydricalcohol or with an aromatic compound such as a phenol or naphthol. Thehydroxy compounds are usually alcohols containing up to about 40aliphatic carbon atoms. These may be monohydric alcohols such asmethanol, ethanol, isooctanol, dodecanol, cyclohexanol, neopentylalcohol, monomethyl ether of ethylene glycol and the like, or polyhydricalcohols including ethylene glycol, diethylene glycol, dipropyleneglycol, tetramethylene glycol, pentaerythritol, glycerol and the like.Carbohydrates (e.g., sugars, starches, cellulose) are also suitable asare partially esterified derivatives of polyhydric alcohols having atleast three hydroxy radicals. Aliphatic polyols containing up to 10carbon atoms and at least 3 hydroxy groups, especially those with up to6 carbon atoms and 3-6 hydroxy groups, are preferred.

The esterification reaction is usually effected at a temperature aboveabout 100° C. and typically at 150°-300° C. The esters may be neutral oracidic, or may contain unesterified hydroxy groups, according as theratio of equivalents of acid-producing compound to hydroxy compound isequal to, greater than or less than 1:1.

It is possible to prepare mixed oxygen- and nitrogen-bridged dispersantsby reacting the acylating agent simultaneously or, preferably,sequentially with nitrogen-containing and hydroxy reagents such as thosepreviously described. The relative amounts of the nitrogen-containingand hydroxy reagents may be between about 10:1 and 1:10, on anequivalent weight basis. The methods of preparation of the mixed oxygen-and nitrogen-bridged dispersants are generally the same as for theindividual dispersants described, except that two sources of radical IIare used. Mixtures of independently prepared dispersants are alsosuitable. Mixed dispersants of these types are frequently preferred forthe purposes of this invention.

Typical carboxylic dispersants suitable for use as reagent B are listedin the following table. "Reagent I" and "Reagent II" are, respectively,the sources of radicals I and II as previously defined.

                                      TABLE I                                     __________________________________________________________________________                                       Ratio of                                                                            Reaction                                                                equivalents,                                                                        temperature,                         Example                                                                            Reagent I     Reagent II      I:II  °C.                                                                           Diluent                       __________________________________________________________________________    1    Polyisobutenyl (mol. wt.                                                                    Polyethylene amine mixture                                                                    0.48  150    Mineral oil                        about 900) succinic an-                                                                     containing about 3-7 amino                                      hydride prepared from                                                                       groups per molecule                                             chlorinated polyisobutene                                                2    Same as Example 1                                                                           Pentaethylene hexamine                                                                        0.41  150    Mineral oil                   3    Like Example 1 except                                                                       Pentaethylene hexamine                                                                        0.61  150    Mineral oil                        polyisobutene mol. wt.                                                        is about 1050                                                            4    Like Example 1, except                                                                      Diethylene triamine                                                                           1.0   150    Mineral oil                        polyisobutene mol. wt. is                                                     about 850                                                                5    Same as Example 4                                                                           Ethylene diamine                                                                              1.0   150    Mineral oil                   6    Same as Example 4                                                                           Di-(1,2-propylene)triamine                                                                    1.0   180-190                                                                              Mineral oil-                                                                  toluene                       7    Same as Example 4                                                                           N-(2-hydroxyethyl)-                                                                           1.06  150-155                                                                              Mineral oil                                      trimethylene diamine                                       8    Same as Example 1                                                                           Pentaerythritol, followed by                                                                  0.79  205-215                                                                              Xylene                                           polyethylene amine of                                                         Example 1 (ratio of equiva-                                                   lents 3.4:1)                                               9    Same as Example 1                                                                           Same as Example 1                                                                             0.67  150    Mineral oil                   10   Same as Example 1                                                                           Same as Example 1                                                                             1.33  150    Mineral oil                   11   Like Example 1, except                                                                      Pentaerythritol, followed by                                                                  0.44  150-210                                                                              Mineral oil                        polyisobutene mol. wt.                                                                      polyethylene amine of Example 1                                 is about 1100 (ratio of equivalents 7.7:1)                               12   Acid produced by reaction                                                                   Ethylene diamine                                                                              2.0   150    Xylene                             of chlorinated (3.6% Cl)                                                      polyisobutene (mol. wt.                                                       750) with KCN, followed                                                       by hydrolysis                                                            13   Methyl ester produced                                                                       Triethylene tetramine                                                                         1.0   140-220                                                                              --                                 by reaction of chlorinated                                                    (4.7% Cl) polyisobutene                                                       (mol. wt. 1000) with methyl                                                   methacrylate                                                             14   Reaction product of sodio-                                                                  Same as Example 1                                                                             0.4   150    Xylene                             malonic ester with C.sub.75                                                   brominated wax                                                           15   Reaction product of                                                                         Pentaethylene hexamine                                                                        0.8   180-200                                                                              --                                 chlorinated (4.5% Cl) poly-                                                   isobutene (mol. wt. 850)                                                      with acrylic acid                                                        16   Acid produced by haloform                                                                   Same as Example 1                                                                             0.8   180-210                                                                              --                                 reaction with methyl                                                          heptacontanyl ketone                                                     17   Same as Example 11                                                                          Pentaerythritol 0.5   150-210                                                                              Mineral oil                   18   Like Example 1, except                                                                      Neopentyl glycol                                                                              1.0   240-250                                                                              --                                 polyisobutene mol. wt.                                                        is about 1000                                                            19   Same as Example 18                                                                          Methanol*       Excess                                                                              50-65  Toluene                                                          methanol                                   20   Same as Example 18                                                                          Polyethylene glycol                                                                           2.0   240-250                                                                              --                                               (mol. wt. about 600)                                       21   Same as Example 18                                                                          Oleyl alcohol** 1.0   150-173                                                                              Xylene                        22   Like Example 15, except                                                                     Sorbitol        0.48  115-205                                                                              Mineral oil                        polyisobutene mol. wt.                                                        is about 982                                                             23   Same as Example 22                                                                          Pentaerythritol 1.0   180-205                                                                              --                            24   Reaction product of poly-                                                                   Mannitol        0.33  115-205                                                                              Mineral oil                        isobutene (mol. wt. 1500)                                                     with chloroacetyl chloride                                               __________________________________________________________________________     *Hydrogen chloride catalyst                                                   **pToluenesulfonic acid catalyst                                         

The compositions of this invention are prepared by merely mixing thedesired monomer or monomer mixture with the dispersant and allowing freeradical polymerization to take place. A substantially inert diluent isgenerally used; suitable diluents include such non-polar materials asmineral oil, benzene, toluene, xylene, hexane, heptane and petroleumnaphtha; analogous halogenated hydrocarbons such as chlorobenzene;ethers, and the like. The polymerization is ordinarily initiated by oneor more free radical polymerization catalysts such as benzoyl peroxide,tertiary butyl hydroperoxide, acetyl peroxide, hydrogen peroxide,azobisisobutyronitrile, isopropyl peroxydicarbonate,persulfate-bisulfite, persulfate-sodium formaldehyde sulfoxylate,chlorate-sulfite and the like, but may also be initiated by irradiation.

The temperature of polymerization is not critical. Usually, thepolymerization reaction is carried out between room temperature andabout 125° C., preferably about 30°-90° C.

Likewise, the proportions of reagents A and B are not critical.Generally, enough of reagent B is used to produce a stable solution ordispersion of the polymer in the diluent. For this purpose, the weightratio of reagent B to reagent A may be as high as about 6:1 or as low asabout 0.1:1. Weight ratios between about 0.8:1 and 4:1 are preferred.

Following completion of the polymerization reaction, the product may berecovered by conventional means, typically by removal of solvent byevaporation. However, diluent removal is frequently unnecessary toremove the diluent and in certain instances, as when the diluent ismineral oil or a similar non-volatile material, may be inadvisable.

The exact chemical nature of the compositions of this invention is notknown with certainty. The polymer of reagent A constitutes a substantialportion of the product; said polymer may be a separate molecular entityfrom the dispersant (reagent B) which may merely serve to disperse orsuspend the same, or there may be some percentage of grafting of thepolymer chain on the dispersant, as through the aliphatic portionthereof. A complete definition of the compositions of this invention,however, is possible only in terms of the method of their preparation.

The preparation of the compositions of this invention is illustrated bythe following examples. All parts and percentages are by weight unlessotherwise indicated.

EXAMPLE 25

Styrene, 175 grams, is mixed with 325 grams of a 60% mineral oilsolution of the dispersant of Example 10 in a nitrogen atmosphere. Asolution of 0.12 gram of azobisisobutyronitrile in 5 ml. of benzene isadded and the mixture is stirred at 70°-73° C. for about 45 minutes.Stirring is continued at this temperature for 4 hours, during whichperiod four additional 0.12-gram portions of azobisisobutyronitrile (inbenzene solution) are added. The product is the desired composition,obtained as a 66% solution in mineral oil.

EXAMPLE 26

To a mixture of 24.5 grams of styrene and 45.5 grams of a 56% solutionin mineral oil of the dispersant of Example 17 is added 1 ml. of a 10%heptane solution of isopropyl peroxydicarbonate. The reaction mixture isflushed with nitrogen, sealed in a bottle and agitated at 40° C. for 20hours. An additional 1 ml. of the isopropyl peroxydicarbonate solutionis then added and agitation is continued for an additional 24 hours at40° C. The product is the desired composition (64% solution in mineraloil).

EXAMPLE 27

A mixture of 140 grams of styrene, 138 grams of a 56% solution inmineral oil of the dispersant of Example 17, and 247 grams of white oilis purged with nitrogen and heated to 75° C. A solution of 0.14 gram ofbenzoyl peroxide in 3 ml. of benzene is added and the mixture is stirredat 77°-78° C. for 11/2 hours. Stirring is continued at this temperaturefor 9 hours as four additional portions of benzoyl peroxide solution areadded. The traces of volatile material which are present are thenremoved by vacuum stripping at 80° C., yielding the desired product asthe residue.

EXAMPLE 28

A mixture of 120 grams of acrylonitrile and 223 grams of a 60% solutionin mineral oil of the dispersant of Example 9 is heated to 70° C. withstirring, and a solution of 0.12 gram of azobisisobutyronitrile in 5 ml.of benzene is added. Stirring is continued for 6 hours, during whichtime an additional 4 portions of azobisisobutyronitrile solution areadded. At the end of this time 200 grams of mineral oil is added andvolatiles are removed by vacuum stripping, yielding the desired productas the residue.

EXAMPLE 29

A mixture is prepared containing 12.5 grams of the dispersant of Example8 (solvent-free) and 212.5 grams of a blend of 88.5% (by weight)diisodecyl azelate and 11.5% isodecyl pelargonate. The mixture is heatedto 70° C. and purged with nitrogen, and 25 grams of acrylonitrile isadded followed by a solution of 0.05 gram of azobisisobutyronitrile in 5ml. of benzene. The mixture is stirred for 1/2 hour, after which anadditional portion of the azobisisobutyronitrile solution is added.Stirring is continued for 21/2 hours, after which volatile materials areremoved by vacuum stripping to yield the desired product as the residue.

EXAMPLE 30

A mixture of 19.5 grams of a 64.7% solution in xylene of the dispersantof Example 8, 50 grams of acrylonitrile and 187.5 grams of Stoddardsolvent is purged with nitrogen and heated to 70° C. A solution of 0.05gram of azobisisobutyronitrile in 5 ml. of benzene is added and themixture is stirred for 4 hours at 70°-75° C., yielding the desiredproduct.

EXAMPLE 31

A mixture of 262.5 grams of acrylonitrile and 487.5 grams of a 56%solution in mineral oil of the dispersant of Example 17 is purged withnitrogen and heated to 70° C. A solution of 0.25 gram of benzoylperoxide in 5 ml. of benzene is added, and the mixture is stirred for1/2 hour at 70°-78° C. Stirring is continued at this temperature forabout 61/2 hours, during which time four additional portions of benzoylperoxide solution are added. Benzene, 25 ml., is added and volatilematerials are removed by vacuum stripping to yield the desired productas the residue.

EXAMPLE 32

A mixture of 325 grams of a 60% mineral oil solution of the dispersantof Example 10 and 175 grams of diacetone acrylamide is purged withnitrogen and heated to 65° C. A solution of 0.12 gram ofazobisisobutyronitrile in 5 ml. of benzene is added and the mixture isstirred for 45 minutes at 66°-77° C. Stirring at this temperature iscontinued for about 5 hours, during which time 4 additional 0.12-gramportions of azobisisobutyronitrile (in benzene solution) are added.Volatile materials are then removed by vacuum stripping, yielding thedesired product as the residue.

EXAMPLE 33

An ester-dispersant mixture identical with that of Example 29 isprepared and heated to 70°-75° C. under nitrogen. Diacetone acrylamide,25 grams, is added, followed by a solution of 0.05 gram ofazobisisobutyronitrile in 5 ml. of benzene. The mixture is stirred at70°-75° C. for 4 hours, after which volatile materials are removed byvacuum stripping, yielding the desired product as the residue.

EXAMPLE 34

A mixture of 31 grams of a 64.7% solution in xylene of the dispersant ofExample 8, 80 grams of diacetone acrylamide and 175 grams of Stoddardsolvent is purged with nitrogen and heated to 70° C. A solution of 0.05gram of azobisisobutyronitrile in 5 ml. of benzene is added and themixture is stirred for 4 hours at 70°-80° C., yielding the desiredproduct.

EXAMPLE 35

A mixture of 162 grams of diacetone acrylamide and 300 grams of a 56%solution in mineral oil of the dispersant of Example 17 is purged withnitrogen and heated to 65° C. A solution of 0.1 gram of benzoyl peroxidein 5 ml. of benzene is added, and the mixture is stirred for 1/2 hour at78°-81° C. Stirring is continued at this temperature for about 51/2hours, during which time four additional portions of benzoyl peroxidesolution are added. Volatile materials are then removed by vacuumstripping to yield the desired product as the residue.

EXAMPLE 36

A mixture of 250 grams of n-butyl acrylate and 750 grams of a 60%mineral oil solution of the dispersant of Example 1 is purged withnitrogen and heated to 70° C. A solution of 1 gram ofazobisisobutyronitrile in 10 ml. of benzene is added and the mixture isstirred for 11/2 hours at 70°-80° C. Stirring is continued for 81/2hours, during which time benzene solutions of two additional 0.5-gramportions, and finally of a 1.0-gram portion, of azobisisobutyronitrileare added. Volatile materials are then removed by vacuum stripping andthe residue is diluted with 105 grams of mineral oil and filtered toyield the desired product.

EXAMPLE 37

A mixture of 50 grams of N-vinylpyrrolidone and 450 grams of a 56%solution in mineral oil of the dispersant of Example 17 is purged withnitrogen and heated to 70° C. A solution of 0.1 gram ofazobisisobutyronitrile in 5 ml. of benzene is added and the mixture isstirred for 1 hour at 70°-75° C. Stirring at this temperature iscontinued for 41/2 hours as 3 additional portions ofazobisisobutyronitrile solution are added. The mixture is stirred for anadditional 2 hours at 78°-80° C. and then volatile materials are removedby vacuum stripping, yielding the desired product as the residue.

EXAMPLE 38

Following the procedure of Example 36, a product is prepared from 30grams of N-vinylthiopyrrolidone, 270 grams of a mineral oil solution ofthe dispersant of Example 17, and a solution of 0.2 gram ofazobisisobutyronitrile in 20 ml. of benzene (added in 4 increments).

EXAMPLE 39

A mixture of 14 grams of vinyl acetate and 56 grams of a 56% solution inmineral oil of the dispersant of Example 17 is placed in a high-pressurebottle, and 1 ml. of a 10% heptane solution of isopropylperoxydicarbonate is added. The bottle is flushed with nitrogen, cappedand shaken at 40° C. for 20 hours. An additional 1 ml. of isopropylperoxydicarbonate solution is added and agitation is continued for 24hours at 40° C. The mixture is vacuum stripped to yield the desiredproduct as the residue.

EXAMPLE 40

A mixture of 150 grams of diacetone acrylamide, 8 grams of acrylamide,62 grams of a 64.7% solution in xylene of dispersant of Example 8, and350 grams of Stoddard solvent is purged with nitrogen and heated to 70°C. A solution of 0.1 gram of azobisisobutyronitrile in 5 ml. of benzeneis added and the mixture is stirred at 70°-80° C. for 4 hours to yieldthe desired product.

EXAMPLE 41

A mixture of 80 grams of diacetone acrylamide, 80 grams ofacrylonitrile, 62 grams of a 64.7% solution in xylene of the dispersantof Example 8, and 350 grams of Stoddard solvent is purged with nitrogenand heated to 70° C. A solution of 0.1 gram of azobisisobutyronitrile in5 ml. of benzene is added and the mixture is stirred at 70°-80° C. for 4hours. A small amount of solid separates and the liquid is decantedtherefrom; the liquid constitutes the desired product.

EXAMPLE 42

A mixture of 250 grams of a 56% solution in mineral oil of thedispersant of Example 17, 175 grams of N-vinyl-pyrrolidone, 45 grams ofa mixture of C₁₂₋₁₄ dialkyl fumarates and 167 grams of mineral oil ispurged with nitrogen and heated to 70° C. A solution of 2 grams ofazobisisobutyronitrile in 40 ml. of benzene is prepared and added in 4equal increments at 1-hour intervals. Following the addition of thefinal portion of azobisisobutyronitrile, the mixture is stirred for 2hours at 78°-82° C. and is then vacuum stripped, yielding the desiredproduct as the residue.

As previously mentioned, the compositions of this invention are usefulas multi-purpose additives in lubricants, fuels and functional fluids,to improve dispersancy and at the same time extreme pressure propertiesor viscosity. They can be employed in a variety of lubricatingcompositions, and functional fluids based on diverse oils of lubricatingviscosity, including natural and synthetic lubricating oils and mixturesthereof. The lubricating compositions contemplated include crankcaselubricating oils for spark-ignited and compression-ignited internalcombustion engines including automobile and truck engines, two-cycleengine lubricants, aviation piston engines, marine and railroad dieselengines, and the like, as well as automatic transmission fluids,transaxle lubricants, gear lubricants, metal-working lubricants,hydraulic fluids, and other lubricating oil and grease compositions.

Natural oils include animal oils and vegetable oils (e.g., castor oil,lard oil) as well as solvent-refined or acid-refined mineral lubricatingoils of the paraffinic, naphthenic, or mixed paraffinic-naphthenictypes. Oils of lubricating viscosity derived from coal or shale are alsouseful base oils. Synthetic lubricating oils include hydrocarbon oilsand halo-substituted hydrocarbon oils such as polymerized andinterpolymerized olefins (e.g., polybutylenes, polypropylenes,propylene-isobutylene copolymers, chlorinated polybutylenes, etc.);alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzene,dinonylbenzenes, di-(2-ethylhexyl) benzenes, etc.); polyphenyls (e.g.,biphenyls, terphenyls, etc.); and the like. Alkylene oxide polymers andinterpolymers and derivatives thereof where the terminal hydroxyl groupshave been modified by esterification, etherification, etc., constituteanother class of known synthetic lubricating oils. These are exemplifiedby the oils prepared through polymerization of ethylene oxide orpropylene oxide, the alkyl and aryl ethers of these polyoxyalkylenepolymers (e.g., methylpolyisopropylene glycol ether having an averagemolecular weight of 1000, diphenyl ether of polyethylene glycol having amolecular weight of 500-1000, diethyl ether of polypropylene glycolhaving a molecular weight of 1000-1500, etc.) or mono- andpolycarboxylic esters thereof, for example, the acetic acid esters,mixed C₃ -C₈ fatty acid esters, or the C₁₃ Oxo acid diester oftetraethylene glycol. Another suitable class of synthetic lubricatingoils comprises the esters of dicarboxylic acids (e.g., phthalic acid,succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid,fumaric acid, adipic acid, linoleic acid dimer, etc.) with a variety ofalcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol,2-ethylhexyl alcohol, etc.). Specific examples of these esters includedibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, the complex ester formed by reacting one mole ofsebacic acid with two moles of tetraethylene glycol and two moles of2-ethylhexanoic acid, and the like. Silicon-based oils such as thepolyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils andsilicate oils comprise another useful class of synthetic lubricants(e.g., tetraethyl silicate, tetraisopropyl silicate,tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-tetraethyl) silicate,tetra-(p-tert-butylphenyl) silicate,hexyl-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes,poly(methylphenyl)-siloxanes, etc.). Other synthetic lubricating oilsinclude liquid esters of phosphorus-containing acids (e.g., tricresylphosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid,etc.), polymeric tetrahydrofurans, and the like.

In general, about 0.05-20.0 parts (by weight) of the composition of thisinvention is dissolved or stably dispersed in 100 parts of oil toproduce a satisfactory fluid. The invention also contemplates the use ofother additives in combination with the products of this invention. Suchadditives include, for example, detergents and dispersants of theash-producing or ashless type, oxidation inhibiting agents, pour pointdepressing agents, extreme pressure agents, color stabilizers andanti-foam agents.

The ash-producing detergents are exemplified by oil-soluble neutral andbasic salts of alkali or alkaline earth metals with sulfonic acids,carboxylic acids, or organic phosphorus acids characterized by at leastone direct carbon-to-phosphorus linkage such as those prepared by thetreatment of an olefin polymer (e.g., polyisobutene having a molecularweight of 1000) with a phosphorizing agent such as phosphorustrichloride, phosphorus heptasulfide, phosphorus pentasulfide,phosphorus trichloride and sulfur, white phosphorus and a sulfur halide,or phosphorothioic chloride. The most commonly used salts of such acidsare those of sodium, potassium, lithium, calcium, magnesium, strontiumand barium.

The term "basic salt" is used to designate metal salts wherein the metalis present in stoichiometrically larger amounts than the organic acidradical. The commonly employed methods for preparing the basic saltsinvolve heating a mineral oil solution of an acid with a stoichiometricexcess of a metal neutralizing agent such as the metal oxide, hydroxide,carbonate, bicarbonate, or sulfide at a temperature above 50° C. andfiltering the resulting mass. The use of a "promoter" in theneutralization step to aid the incorporation of a large excess of metallikewise is known. Examples of compounds useful as the promoter includephenolic substances such as phenol, naphthol, alkylphenol, thiophenol,sulfurized alkylphenol, and condensation products of formaldehyde with aphenolic substance; alcohols such as methanol, 2-propanol, octylalcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, andcyclohexyl alcohol; and amines such as aniline, phenylenediamine,phenothiazine, phenyl-β-naphthylamine, and dodecylamine. A particularlyeffective method for preparing the basic salts comprises mixing an acidwith an excess of a basic alkaline earth metal neutralizing agent and atleast one alcohol promoter, and carbonating the mixture at an elevatedtemperature such as 60°-200° C.

Ashless detergents and dispersants are illustrated by the interpolymersof an oil-solubilizing monomer, e.g., decyl methacrylate, vinyl decylether, or high molecular weight olefin, with a monomer containing polarsubstituents, e.g., aminoalkyl acrylate orpoly-(oxyethylene)-substituted acrylate; the amine salts, amides, andimides of oil-soluble monocarboxylic or dicarboxylic acids such asstearic acid, oleic acid, tall oil acid, and high molecular weight alkylor alkenyl-substituted succinic acid. Especially useful are thecompositions described hereinabove as useful as reagent B.

Extreme pressure agents and corrosion-inhibiting andoxidation-inhibiting agents are exemplified by chlorinated aliphatichydrocarbons such as chlorinated wax; organic sulfides and polysulfidessuch as benzyl disulfide, bis(chlorobenzyl) disulfide, dibutyltetrasulfide, sulfurized methyl ester of oleic acid, sulfurizedalkylphenol, sulfurized dipentene, and sulfurized terpene;phosphosulfurized hydrocarbons such as the reaction product of aphosphorus sulfide with turpentine or methyl oleate; phosphorus estersincluding principally dihydrocarbon and trihydrocarbon phosphites suchas dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentyl phenyl phosphite, tridecyl phosphite,distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenylphosphite, polypropylene (molecular weight 500)-substituted phenylphosphite, diisobutyl-substituted phenyl phosphite; metalthiocarbamates, such as zinc dioctyldithiocarbamate, and bariumheptylphenyl dithiocarbamate; Group II metal phosphorodithioates such aszinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate,barium di(heptylphenyl)phosphorodithioate, cadmiumdinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acidproduced by the reaction of phosphorus pentasulfide with an equimolarmixture of isopropyl alcohol and n-hexyl alcohol.

The compositions of this invention can be added directly to thelubricant or functional fluid or they can be diluted with an inertdiluent such as mineral oil to form an additive concentrate. Theseconcentrates generally contain about 20-90% by weight of the compositionof this invention and may contain, in addition, one or more of the otheradditives described hereinabove.

Typical lubricating compositions of this invention are listed in thefollowing table. Except for the values for mineral oil and for theproducts of Examples 25, 28, 32 and 41, all amounts are exclusive ofmineral oil used as diluent.

    ______________________________________                                                       Parts by weight                                                               Lubricant                                                      Ingredient       A       B       C     D                                      ______________________________________                                        Mineral oil      89.34   90.49   89.34 90.49                                   (SAE 10W-30 base)                                                            Product of Example 25                                                                          6.62    --      --    --                                     Product of Example 28                                                                          --      6.62    --    --                                     Product of Example 32                                                                          --      --      6.62  --                                     Product of Example 41                                                                          --      --      --    6.62                                   Dispersant of Example 17                                                                       1.73    0.58    1.73  1.73                                   Basic calcium petroleum                                                                        0.97    0.97    0.97  0.97                                    sulfonate                                                                    Zinc salt of mixture of                                                        isobutyl- and primary                                                         amylphosphorodithioic acids                                                                   0.84    0.84    0.84  0.84                                   Sulfurized copolymer of                                                        butadiene and                                                                butyl acrylate   0.50    0.50    0.50  0.50                                   Silicone anti-foam agent                                                                        0.004   0.004   0.004                                                                               0.004                                 ______________________________________                                    

The compositions of this invention are also useful as thickeners andanti-sag agents for alkyd and epoxy paints and for unsaturated polyestersystems. For example, addition of 4 parts by weight of the product ofExample 31 to 100 parts of a solution in styrene of an unsaturatedpolyester derived from phthalic acid causes about a two-fold increase inBrookfield viscosity.

What is claimed is:
 1. A method for preparing a composition of matterwhich comprises polymerizing, under free radical polymerizationconditions and at a temperature of about 30°-90° C., (A) at least oneethylenically unsaturated monomer having from 3 to about 10 carbon atomsand a terminal olefinic bond and selected from the group consisting ofunsaturated monohydric or polyhydric alcohols, carboxylic acid estersthereof, esters of unsaturated carboxylic acids and saturated alcohols,vinyl cyclic compounds, unsaturated ethers, unsaturated ketones, amidesof unsaturated carboxylic acids, unsaturated aliphatic hydrocarbons,alkenyl halides and unsaturated nitriles; in the presence of (B) atleast one oil-soluble dispersant incapable of addition polymerizationand characterized by the presence within its molecular structure of anacyl or acylimidoyl radical containing at least about 34 carbon atomsand an oxygen atom attached directly to said acyl or acylimidoylradical, said oxygen atom also being attached to a hydrocarbon radicalor a substituted hydrocarbon radical in which the substituents do notalter significantly the character or reactivity of the radical andcomprise no more than about 10% by weight of said radical.
 2. A methodaccording to claim 1 wherein said monomer A is at least one vinylaromatic compound, vinyl-substituted heterocyclic compound containing anitrogen atom as part of the heterocyclic ring, vinyl ester of acarboxylic acid, or ester, amide or nitrile of acrylic or methacrylicacid.
 3. A method according to claim 2 wherein said dispersant B isprepared by the reaction of a succinic acid or anhydride containing asubstantially saturated hydrocarbon-substituted orhalohydrocarbon-substituted substituent with at least one alcohol.
 4. Amethod according to claim 3 wherein the substituent on the succinic acidor anhydride contains at least about 50 carbon atoms.
 5. A methodaccording to claim 4 wherein said monomer A is at least one compoundselected from the group consisting of styrene, acrylonitrile anddiacetone acrylamide.
 6. A composition prepared by the method of any ofclaims 1-5.